CN109666360B - Preparation method of graphene oxide modified polymer cement-based anticorrosive paint - Google Patents

Preparation method of graphene oxide modified polymer cement-based anticorrosive paint Download PDF

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CN109666360B
CN109666360B CN201811490912.6A CN201811490912A CN109666360B CN 109666360 B CN109666360 B CN 109666360B CN 201811490912 A CN201811490912 A CN 201811490912A CN 109666360 B CN109666360 B CN 109666360B
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graphene oxide
cement
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CN109666360A (en
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赵丕琪
刘红花
黄永波
王守德
孙传奎
宫晨琛
芦令超
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Qingdao Weili Commercial Concrete Co ltd
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University of Jinan
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Abstract

The invention provides a preparation method of a graphene oxide modified polymer cement-based anticorrosive paint, which comprises the following steps: carboxylating graphene oxide; synthesizing a graphene oxide modified polyacrylate emulsion; and (3) preparing the graphene oxide modified polymer cement-based anticorrosive paint. The coating prepared by the preparation method has the advantages of high toughness, high bonding strength, high compactness and the like of the organic polymer, and also has high mechanical strength and high weather resistance and durability of the special cement-based material. The graphene oxide is used for modifying the polymer cement-based anticorrosive coating, so that the mechanical property of a polymer film is further optimized, and the interface compatibility and the adhesive force of a polymer organic component and a cement-based inorganic component are improved, so that the microstructure of the coating is optimized, and the anticorrosive property and the stability are improved.

Description

Preparation method of graphene oxide modified polymer cement-based anticorrosive paint
Technical Field
The invention designs a cement-based anticorrosive coating, and particularly relates to a preparation method of a graphene oxide modified polymer cement-based anticorrosive coating.
Background
The polymer cement-based paint is a waterproof paint formed by compounding high-molecular polymer emulsion (one or more of polypropylene emulsion, styrene-acrylic emulsion, silicone-acrylic emulsion, polyacrylate emulsion and VAE emulsion), sulphoaluminate cement, pigments and fillers (one or more of basalt, talcum powder, silicon dioxide, heavy calcium, fly ash and metakaolin) and various additives (defoaming agent, preservative, dispersing agent and film-forming assistant), and is a two-component paint which has high toughness of high-molecular polymer materials and good durability of inorganic materials.
Graphene is a two-dimensional carbon nanomaterial consisting of carbon atoms in sp hybridized orbitals in a hexagonal honeycomb lattice. The graphene has excellent thermal conductivity, electrical conductivity and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future.
The oxide of graphene oxide and graphene is a product obtained by chemically oxidizing and stripping graphite powder. The two-dimensional space plane lamellar structure has rich oxygen-containing groups distributed on the surface and the edge, and can be expanded to tens of microns in transverse dimension at any time.
The existing polymer cement-based coating has the defects of low mechanical strength, poor wear resistance, low compactness, insufficient corrosion resistance and the like, the service life is greatly reduced, the protective effect can not be well exerted, and the performance requirement of long-acting corrosion resistance of the coating is difficult to meet when the coating is applied to a severe environment.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a graphene oxide modified polymer cement-based anticorrosive coating. The coating prepared by the preparation method has the advantages of high toughness, high bonding strength, high compactness and the like of the organic polymer, and also has high mechanical strength and high weather resistance and durability of the special cement-based material. The graphene oxide is used for modifying the polymer cement-based anticorrosive coating, so that the mechanical property of a polymer film is further optimized, and the interface compatibility and the adhesive force of a polymer organic component and a cement-based inorganic component are improved, so that the microstructure of the coating is optimized, and the anticorrosive property and the stability are improved. Firstly, modifying a polyacrylate emulsion by using graphene oxide, and grafting the graphene oxide to the emulsion. And then compounding the polyacrylate emulsion containing the graphene oxide with other substances such as cement and the like to prepare the long-acting anticorrosion polymer cement-based anticorrosive coating.
The invention is realized by the following technical scheme:
a preparation method of a graphene oxide modified polymer cement-based anticorrosive paint comprises the following steps:
(1) carboxylation of graphene oxide
And adding 10-20 parts of graphene oxide into 50-60 parts of 0.5mol/L sodium hydroxide alkali solution, and performing ultrasonic dispersion for 2 hours. Then 5-10 parts of chloroacetic acid is added, and ultrasonic dispersion is carried out for 1-2 h. And finally, performing suction filtration and separation on the product by using a 0.22-micron PTFE filter membrane, repeatedly centrifuging and washing the filter cake to be neutral to remove impurities, and drying the obtained product at 45 ℃ for 12 hours under a vacuum condition to obtain a homogeneous carboxylated graphene oxide solution.
(2) Synthesis of graphene oxide modified polyacrylate emulsion
Uniformly stirring 1-3 parts of anionic emulsifier, 1-3 parts of nonionic emulsifier and 30-40 parts of deionized water, adding 50-60 parts of acrylic monomer, and magnetically stirring for 30min to obtain a pre-emulsion for later use;
2-3 parts of anionic emulsifier, 1-3 parts of nonionic emulsifier, 2-5 parts of pH regulator and 30-50 parts of deionized water are magnetically stirred for 20min, and the mixture is heated to 70 ℃ in a water bath. Then adding 0.5-2 parts of initiator and pre-emulsified emulsion, controlling the dropwise adding within 3h, beginning dropwise adding 5-8 parts of diluted carboxylated graphene oxide solution when one third of the pre-emulsified solution is left, finishing the adding for 20min, keeping the temperature at 60 ℃ for 2h after all raw materials are completely dropwise added, cooling to room temperature, filtering and discharging, and adjusting the pH value to 7-8 by using ammonia water to obtain the required graphene oxide modified polyacrylate emulsion;
(3) preparation of graphene oxide modified polymer cement-based anticorrosive paint
50-80 parts of sulphoaluminate cement, 20-30 parts of silicon dioxide, 20-30 parts of talcum powder, 2-5 parts of zinc phosphate and 2-5 parts of mica powder are placed in a stirrer to be stirred for 10-15min to obtain mixed powder, 60-80 parts of graphene oxide modified polyacrylate emulsion, 20-40 parts of deionized water and 1-2 parts of defoaming agent are placed in the stirrer to be stirred for 3-5min, then the mixed powder is added, 1-3 parts of defoaming agent, 0.5-2 parts of dispersing agent, 1-2 parts of water reducing agent and 2-5 parts of film forming auxiliary agent are sequentially added to be stirred for 15min, and finally the prepared slurry is placed in an ultrasonic disperser to be dispersed for 5min to obtain the cement-based anticorrosive coating.
And further optimizing the dispersion between the liquid and the solid by utilizing cavitation reaction, reducing bubbles in the slurry, brushing or spraying the prepared coating on a cement substrate to a thickness of 0.5-1mm, and brushing or spraying for the second time after the surface is dried to obtain a polymer cement-based anticorrosive coating containing graphene oxide, wherein the total thickness of the coating is 2 mm.
Preferably, the acrylic monomer is one or more of methyl methacrylate, methyl acrylate, butyl acrylate and ethyl acrylate;
the anionic emulsifier is sodium dodecyl sulfate or sodium dodecyl benzene sulfonate;
the nonionic emulsifier is OP-10 or OP-20;
the pH regulator is NaHCO3；
The initiator is ammonium persulfate.
Preferably, the water reducing agent is a polycarboxylic acid water reducing agent;
the dispersant is sodium hexametaphosphate;
the film-forming assistant is ester alcohol film-forming assistant;
the defoaming agent is organic silicon defoaming agent.
Advantageous effects
The invention utilizes the excellent mechanical property and the unique two-dimensional structure of the graphene oxide to improve the mechanical property, compactness and corrosion resistance of the coating. Graphite oxideThe alkene has high dispersibility in water, and is rich in various polar oxygen-containing functional groups at the edge, including hydroxyl, carboxyl, epoxy and the like. By utilizing the functional groups, the graphene oxide can be grafted to the polyacrylate emulsion, so that the agglomeration of the graphene oxide in the coating can be reduced, and the mechanical property of the polymer film can be optimized. Carboxyl on the graphene oxide can react with C-S-H and Ca (OH) in cement hydration products2The reaction is carried out to form a stronger covalent bond, thereby not only promoting the hydration of the cement and improving the mechanical property of the coating, but also optimizing the microstructure of the coating, improving the compactness of the coating and increasing the adhesive force between the coating and the cement-based matrix. The graphene oxide sheet has a unique two-dimensional structure, can effectively deflect in a cement-based material, or force cracks to incline and twist around the graphene oxide sheet, so that microcracks of cement are reduced, compactness of the coating is improved, and cracking of the coating is prevented. The sheet structure of the graphene oxide can cut off capillary pores of the coating, prolong the path of corrosive media penetrating into the coating, and increase the corrosion resistance of the coating. In addition, the sulphoaluminate cement with the characteristics of quick hardening and early strength is used as main powder, so that the wear resistance, corrosion resistance and drying speed of the coating can be improved.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
A preparation method of a graphene oxide modified polymer cement-based anticorrosive paint comprises the following steps:
(1) carboxylation of graphene oxide
Adding 15 parts of graphene oxide into 55 parts of 0.5mol/L sodium hydroxide alkali solution, and performing ultrasonic dispersion for 2 hours. Then 8 parts of chloroacetic acid is added, and ultrasonic dispersion is carried out for 1-2 h. And finally, performing suction filtration and separation on the product by using a 0.22-micron PTFE filter membrane, repeatedly centrifuging and washing the filter cake to be neutral to remove impurities, and drying the obtained product at 45 ℃ for 12 hours under a vacuum condition to obtain a homogeneous carboxylated graphene oxide solution.
(2) Synthesis of graphene oxide modified polyacrylate emulsion
Uniformly stirring 2 parts of anionic emulsifier, 2 parts of nonionic emulsifier and 35 parts of deionized water, adding 55 parts of acrylic monomer, and magnetically stirring for 30min to obtain a pre-emulsion for later use;
magnetically stirring 3 parts of anionic emulsifier, 1 part of nonionic emulsifier, 4 parts of pH regulator and 40 parts of deionized water for 20min, and heating in a water bath to 70 ℃. Then adding 1.5 parts of initiator and pre-emulsified emulsion, controlling the dropwise addition within 3h, beginning to dropwise add 8 parts of diluted carboxylated graphene oxide solution when one third of the pre-emulsified solution is left, finishing the addition within 20min, keeping the temperature at 60 ℃ for 2h after all raw materials are completely dropwise added, cooling to room temperature, filtering and discharging, and adjusting the pH value to 7-8 by using ammonia water to obtain the required graphene oxide modified polyacrylate emulsion;
(3) preparation of graphene oxide modified polymer cement-based anticorrosive paint
Placing 70 parts of sulphoaluminate cement, 25 parts of silicon dioxide, 25 parts of talcum powder, 4 parts of zinc phosphate and 4 parts of mica powder in a stirrer, stirring for 10-15min to obtain mixed powder, placing 70 parts of graphene oxide modified polyacrylate emulsion, 30 parts of deionized water and 1.5 parts of defoaming agent in the stirrer, stirring for 3-5min, adding the mixed powder, sequentially adding 2 parts of defoaming agent, 1.5 parts of dispersing agent, 1.5 parts of water reducing agent and 4 parts of film forming auxiliary agent, stirring for 15min, and finally placing the prepared slurry in an ultrasonic dispersion instrument for dispersing for 5min to obtain the cement-based anticorrosive coating.
And further optimizing the dispersion between the liquid and the solid by utilizing cavitation reaction, reducing bubbles in the slurry, brushing or spraying the prepared coating on a cement substrate to a thickness of 0.5-1mm, and brushing or spraying for the second time after the surface is dried to obtain a polymer cement-based anticorrosive coating containing graphene oxide, wherein the total thickness of the coating is 2 mm.
The acrylic monomer is prepared from methyl methacrylate, methyl acrylate, butyl acrylate and ethyl acrylate according to the weight ratio of 0.8: 0.2:0.7:0.3 by weight.
The anionic emulsifier is sodium dodecyl sulfate;
the nonionic emulsifier is OP-10;
the pH regulator is NaHCO3；
The initiator is ammonium persulfate.
The water reducing agent is a polycarboxylic acid water reducing agent;
the dispersant is sodium hexametaphosphate;
the film-forming auxiliary agent is 2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate;
the antifoaming agent used was Foamastar MO 2190AC antifoaming agent.
Example 2
A preparation method of a graphene oxide modified polymer cement-based anticorrosive paint comprises the following steps:
(1) carboxylation of graphene oxide
And adding 20 parts of graphene oxide into 60 parts of 0.5mol/L sodium hydroxide alkali solution, and performing ultrasonic dispersion for 2 hours. Then 10 parts of chloroacetic acid is added, and ultrasonic dispersion is carried out for 1-2 h. And finally, performing suction filtration and separation on the product by using a 0.22-micron PTFE filter membrane, repeatedly centrifuging and washing the filter cake to be neutral to remove impurities, and drying the obtained product at 45 ℃ for 12 hours under a vacuum condition to obtain a homogeneous carboxylated graphene oxide solution.
(2) Synthesis of graphene oxide modified polyacrylate emulsion
Uniformly stirring 1 part of anionic emulsifier, 1 part of nonionic emulsifier and 30 parts of deionized water, adding 50 parts of acrylic monomers, and magnetically stirring for 30min to obtain a pre-emulsion for later use;
magnetically stirring 3 parts of anionic emulsifier, 1 part of nonionic emulsifier, 4 parts of pH regulator and 35 parts of deionized water for 20min, and heating in a water bath to 70 ℃. Then adding 1.5 parts of initiator and pre-emulsified emulsion, controlling the dropwise addition within 3h, beginning to dropwise add 5 parts of diluted carboxylated graphene oxide solution when one third of the pre-emulsified solution is left, finishing the addition within 20min, keeping the temperature at 60 ℃ for 2h after all the raw materials are completely dropwise added, cooling to room temperature, filtering and discharging, and adjusting the pH value to 7-8 by using ammonia water to obtain the required graphene oxide modified polyacrylate emulsion;
(3) preparation of graphene oxide modified polymer cement-based anticorrosive paint
Placing 60 parts of sulphoaluminate cement, 30 parts of silicon dioxide, 30 parts of talcum powder, 3 parts of zinc phosphate and 3 parts of mica powder in a stirrer, stirring for 10-15min to obtain mixed powder, placing 60 parts of graphene oxide modified polyacrylate emulsion, 30 parts of deionized water and 1.5 parts of defoaming agent in the stirrer, stirring for 3-5min, adding the mixed powder, sequentially adding 1.5 parts of defoaming agent, 1.5 parts of dispersing agent, 1.5 parts of water reducing agent and 4 parts of film forming auxiliary agent, stirring for 15min, and finally placing the prepared slurry in an ultrasonic dispersion instrument for dispersing for 5min to obtain the cement-based anticorrosive coating.
And further optimizing the dispersion between the liquid and the solid by utilizing cavitation reaction, reducing bubbles in the slurry, brushing or spraying the prepared coating on a cement substrate to a thickness of 0.5-1mm, and brushing or spraying for the second time after the surface is dried to obtain a polymer cement-based anticorrosive coating containing graphene oxide, wherein the total thickness of the coating is 2 mm.
The acrylic monomer is prepared from methyl methacrylate, methyl acrylate, butyl acrylate and ethyl acrylate according to the weight ratio of 0.8: 0.2:0.6:0.4 by weight.
The anionic emulsifier is sodium dodecyl sulfate;
the nonionic emulsifier is OP-10;
the pH regulator is NaHCO3；
The initiator is ammonium persulfate.
The water reducing agent is a polycarboxylic acid water reducing agent;
the dispersant is sodium hexametaphosphate;
the film-forming auxiliary agent is 2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate;
the antifoaming agent used was Foamastar MO 2190AC antifoaming agent.
Example 3
A preparation method of a graphene oxide modified polymer cement-based anticorrosive paint comprises the following steps:
(1) carboxylation of graphene oxide
And adding 10 parts of graphene oxide into 50 parts of 0.5mol/L sodium hydroxide alkali solution, and performing ultrasonic dispersion for 2 hours. Then 5 parts of chloroacetic acid is added, and ultrasonic dispersion is carried out for 1-2 h. And finally, performing suction filtration and separation on the product by using a 0.22-micron PTFE filter membrane, repeatedly centrifuging and washing the filter cake to be neutral to remove impurities, and drying the obtained product at 45 ℃ for 12 hours under a vacuum condition to obtain a homogeneous carboxylated graphene oxide solution.
(2) Synthesis of graphene oxide modified polyacrylate emulsion
Uniformly stirring 3 parts of anionic emulsifier, 3 parts of nonionic emulsifier and 35 parts of deionized water, adding 60 parts of acrylic monomer, and magnetically stirring for 30min to obtain a pre-emulsion for later use;
magnetically stirring 2 parts of anionic emulsifier, 2 parts of nonionic emulsifier, 4 parts of pH regulator and 40 parts of deionized water for 20min, heating in a water bath to 70 ℃, adding 2 parts of initiator and pre-emulsified emulsion, controlling the dropwise addition within 3h, beginning to dropwise add 6.5 parts of diluted carboxylated graphene oxide solution when one third of the pre-emulsified liquid is left, finishing the addition for 20min, preserving the temperature for 2h at 60 ℃ after all the raw materials are dropwise added, cooling to room temperature, filtering and discharging, and adjusting the pH value to 7-8 by using ammonia water to obtain the required graphene oxide modified polyacrylate emulsion;
(3) preparation of graphene oxide modified polymer cement-based anticorrosive paint
50 parts of sulphoaluminate cement, 25 parts of silicon dioxide, 30 parts of talcum powder, 3 parts of zinc phosphate and 4 parts of mica powder are placed in a stirrer to be stirred for 10-15min to obtain mixed powder, 80 parts of graphene oxide modified polyacrylate emulsion, 20 parts of deionized water and 1.5 parts of defoaming agent are placed in the stirrer to be stirred for 3-5min, then the mixed powder is added, 1.5 parts of defoaming agent, 1.5 parts of dispersing agent, 1 part of water reducing agent and 3 parts of film forming auxiliary agent are sequentially added to be stirred for 15min, and finally the prepared slurry is placed in an ultrasonic dispersion instrument to be dispersed for 5min to obtain the cement-based anticorrosive coating.
And further optimizing the dispersion between the liquid and the solid by utilizing cavitation reaction, reducing bubbles in the slurry, brushing or spraying the prepared coating on a cement substrate to a thickness of 0.5-1mm, and brushing or spraying for the second time after the surface is dried to obtain a polymer cement-based anticorrosive coating containing graphene oxide, wherein the total thickness of the coating is 2 mm.
The acrylic monomer is prepared from methyl methacrylate, methyl acrylate, butyl acrylate and ethyl acrylate according to the weight ratio of 0.8: 0.2:0.8:0.2 by weight.
The anionic emulsifier is sodium dodecyl sulfate;
the nonionic emulsifier is OP-10;
the pH regulator is NaHCO3；
The initiator is ammonium persulfate.
The water reducing agent is a polycarboxylic acid water reducing agent;
the dispersant is sodium hexametaphosphate;
the film-forming auxiliary agent is 2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate;
the antifoaming agent used was Foamastar MO 2190AC antifoaming agent.
Comparative example
A preparation method of a polymer cement-based anticorrosive paint comprises the following steps:
(1) synthesis of polyacrylate emulsion
Uniformly stirring 2 parts of anionic emulsifier, 2 parts of nonionic emulsifier and 35 parts of deionized water, adding 55 parts of acrylic monomer, and magnetically stirring for 30min to obtain a pre-emulsion for later use;
magnetically stirring 3 parts of anionic emulsifier, 1 part of nonionic emulsifier, 4 parts of pH regulator and 35 parts of deionized water for 20min, heating in a water bath to 70 ℃, adding 1.5 parts of initiator and pre-emulsified emulsion, and controlling the dropwise addition within 3 h. After all the raw materials are dripped, preserving heat for 2h at 60 ℃, cooling to room temperature, filtering and discharging, and adjusting the pH value to 7-8 by using ammonia water to obtain the required polyacrylate emulsion;
(2) preparation of polymer cement-based anticorrosive paint
Placing 70 parts of sulphoaluminate cement, 25 parts of silicon dioxide, 25 parts of talcum powder, 4 parts of zinc phosphate and 4 parts of mica powder in a stirrer, stirring for 10-15min to obtain mixed powder, placing 70 parts of polyacrylate emulsion, 30 parts of deionized water and 1.5 parts of defoaming agent in the stirrer, stirring for 3-5min, adding the mixed powder, sequentially adding 1.5 parts of defoaming agent, 1.5 parts of dispersing agent, 1.5 parts of water reducing agent and 4 parts of film forming auxiliary agent, stirring for 15min, and finally placing the prepared slurry in an ultrasonic disperser for dispersing for 5min to obtain the cement-based anticorrosive coating.
And further optimizing the dispersion between the liquid and the solid by utilizing cavitation reaction, reducing bubbles in the slurry, brushing or spraying the prepared coating on a cement substrate to a thickness of 0.5-1mm, and brushing or spraying for the second time after the surface is dried to obtain a polymer cement-based anticorrosive coating containing graphene oxide, wherein the total thickness of the coating is 2 mm.
The acrylic monomer is prepared from methyl methacrylate, methyl acrylate, butyl acrylate and ethyl acrylate according to the weight ratio of 0.8: 0.2:0.6:0.4 by weight.
The anionic emulsifier is sodium dodecyl sulfate;
the nonionic emulsifier is OP-10;
the pH regulator is NaHCO3；
The initiator is ammonium persulfate.
The water reducing agent is a polycarboxylic acid water reducing agent;
the dispersant is sodium hexametaphosphate;
the film-forming auxiliary agent is 2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate;
the antifoaming agent used was Foamastar MO 2190AC antifoaming agent.
Performance testing
The polymer sulphoaluminate cement-based anticorrosive coatings prepared in examples 1-3 and comparative example are subjected to various performance tests according to GB/T23445-2009 Polymer Cement waterproofing coating, and the results are shown in Table 1.
Solid content test: weighing the polymer sulphoaluminate cement-based marine anticorrosive paint, placing the paint in a drying oven at 50 +/-2 ℃ for 48 hours, wherein the ratio of the mass after placement to the mass before placement is the solid content of the polymer sulphoaluminate cement-based marine anticorrosive paint.
Tensile strength and elongation at break: and (3) coating the stirred polymer sulphoaluminate cement-based marine anticorrosive paint into a specified mould, standing for 96 hours under the standard condition, and then demoulding. The demolded sample was treated in a (40. + -. 2) ℃ drying oven for 48h and cooled to room temperature. The test piece was cut into a dumbbell shape with a microtome, the tensile properties of the test piece were measured with a universal tester, and the elongation at break of the test piece was calculated.
Bonding strength: coating the polymer sulphoaluminate cement-based marine anticorrosive paint on the surface of a (70 multiplied by 20mm) mortar test block, maintaining for 4 days at room temperature, after 4 days, putting the test block into a drying oven at 40 ℃ to dry the surface completely, then taking out, after putting for 4 hours at room temperature, adding epoxy resin and acetone according to the ratio of 1: 1 mixing to form an adhesive liquid, adhering the drawing block on the adhesive liquid, stably placing the drawing block in the center of the test block, adhering the drawing block in the center of the test block, placing the drawing block in a drying oven at 40 ℃ for drying for 2 days, taking out the drawing block, standing for 4 hours at room temperature, and carrying out bonding strength test.
Impermeability: the prepared polymer sulphoaluminate cement-based marine anticorrosive paint is coated on a mortar test block with the size of 40 multiplied by 160mm, and is placed in a standard cement curing box for curing for 168 hours. And taking out the test block, putting the test block into a permeameter after the surface is dried, increasing the water pressure from 0.2MPa to 0.3MPa after the constant pressure is kept for 2 hours, and increasing the water pressure to 0.1MPa every other hour until the test block is permeable to water. When the impervious test piece is pressurized to 1.5MPa and the constant pressure is 1h, the test piece is still impervious, and the test is stopped.
TABLE 1 Polymer Cement waterproofing paint Performance test results
Figure 138302DEST_PATH_IMAGE002
The polymer sulphoaluminate cement-based anticorrosive coatings prepared in examples 1-3 and comparative example were subjected to coating appearance test according to JTJ275-2000 technical Specification for Corrosion protection of concrete structures in Harbour projects, and the results are shown in Table 2.
Table 2 coating appearance test results
Figure 789863DEST_PATH_IMAGE004
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (3)

1. A preparation method of a graphene oxide modified polymer cement-based anticorrosive paint is characterized by comprising the following steps:
carboxylation of graphene oxide
Adding 10-20 parts of graphene oxide into 50-60 parts of 0.5mol/L sodium hydroxide alkali solution, and performing ultrasonic dispersion for 2 hours; then adding 5-10 parts of chloroacetic acid, and performing ultrasonic dispersion for 1-2 hours; finally, performing suction filtration separation on the product by using a 0.22-micron PTFE filter membrane, repeatedly centrifuging and washing the filter cake to be neutral to remove impurities, and drying the obtained product at 45 ℃ for 12 hours under a vacuum condition to obtain homogeneous carboxylated graphene oxide solution;
synthesis of graphene oxide modified polyacrylate emulsion
Uniformly stirring 1-3 parts of anionic emulsifier, 1-3 parts of nonionic emulsifier and 30-40 parts of deionized water, adding 50-60 parts of acrylic monomer, and magnetically stirring for 30min to obtain a pre-emulsion for later use;
magnetically stirring 2-3 parts of anionic emulsifier, 1-3 parts of nonionic emulsifier, 2-5 parts of pH regulator and 30-50 parts of deionized water for 20min, and heating in water bath to 70 ℃; then adding 0.5-2 parts of initiator and pre-emulsified emulsion, controlling the dropwise addition within 3h, beginning to dropwise add 5-8 parts of carboxylated graphene oxide solution when one third of the pre-emulsified solution is left, finishing the addition within 20min, preserving the temperature at 60 ℃ for 2h after all raw materials are completely dropwise added, cooling to room temperature, filtering and discharging, and adjusting the pH value to 7-8 by using ammonia water to obtain the required graphene oxide modified polyacrylate emulsion;
(3) preparation of graphene oxide modified polymer cement-based anticorrosive paint
Placing 50-80 parts of sulphoaluminate cement, 20-30 parts of silicon dioxide, 20-30 parts of talcum powder, 2-5 parts of zinc phosphate and 2-5 parts of mica powder in a stirrer, stirring for 10-15min to obtain mixed powder, placing 60-80 parts of graphene oxide modified polyacrylate emulsion, 20-40 parts of deionized water and 1-2 parts of defoaming agent in the stirrer, stirring for 3-5min, then adding the mixed powder, sequentially adding 1-3 parts of defoaming agent, 0.5-2 parts of dispersing agent, 1-2 parts of water reducing agent and 2-5 parts of film forming auxiliary agent, stirring for 15min, and finally placing the prepared slurry in an ultrasonic disperser for dispersing for 5min to obtain the cement-based anticorrosive coating;
(4) and carrying out cavitation reaction on the cement-based anticorrosive coating.
2. The preparation method according to claim 1, wherein the acrylic monomer is one or more of methyl methacrylate, methyl acrylate, butyl acrylate and ethyl acrylate;
the anionic emulsifier is sodium dodecyl sulfate or sodium dodecyl benzene sulfonate;
the nonionic emulsifier is OP-10 or OP-20;
the pH regulator is NaHCO3；
The initiator is ammonium persulfate.
3. The preparation method according to claim 1, characterized in that the water reducing agent is a polycarboxylic acid water reducing agent;
the dispersant is sodium hexametaphosphate;
the film-forming assistant is ester alcohol film-forming assistant;
the defoaming agent is organic silicon defoaming agent.
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